KR20230146430A - Polythiol Composition, Polymerizable Composition for Optical Material and Method for Producing Same - Google Patents

Abstract

The present invention relates to the technical field of optical resins, and specifically to polythiol compositions, polymerizable compositions for optical materials, and methods for producing the same. The polythiol composition includes a thiol compound represented by Formula (1) and a compound represented by Formula (2), and the formula for the total amount of the thiol compound represented by Formula (1) and the compound represented by Formula (2): The proportion of the thiol compound represented by 1) is 0.005% to 6%; The polymerizable composition for optical materials includes a polythiol composition, an isocyanate compound, a catalyst, a UV absorber, and a mold release agent; The optical material composition prepared by curing the polymerizable composition for optical materials not only controls the viscosity at the beginning of the polymerization reaction, extends the working time, makes the reaction easier and simpler to perform, but also has excellent optical properties.

Description

Polythiol composition, polymerizable composition for optical material, and method for producing same {Polythiol Composition, Polymerizable Composition for Optical Material and Method for Producing Same}

The present invention relates to the technical field of optical resins, and specifically to polythiol compositions, polymerizable compositions for optical materials, and methods for producing the same.

Plastic materials are light, flexible, and have excellent dyeability, so they have recently been used in the manufacture of various optical materials. In the case of spectacle lenses, low specific gravity, high transparency, low yellowing, high heat resistance, high strength, high refractive index, and high Bebe number are required. High refractive index? Enables wall lenses and high Abbe number enables lower chromatic aberration.

Polythiourethane-based optical resin materials with the above excellent properties have become an important development direction in recent years. This type of resin materials are mainly manufactured using polythiol compounds and isocyanate compounds as raw materials, and the manufacturing process of optical resin lenses and performance metrics have severely limited and impacted development potential and downstream applications. Pre-polymerization (the initial stage of the polymerization reaction) is a very important process in the manufacturing of optical resin lenses. If this step is not well controlled, it will not only cause production abnormalities such as material spraying, but also cause material streaks in the finished product, reducing the qualification ratio of the final product. and the ratio of excellent products decreases. As an important performance index of resin lenses, Abbe number affects the polarization and focus of light. The higher the value, the less distortion and the better the light transmittance of the lens. However, the refractive index of the lens decreases as the Abbe number increases, and it is difficult to achieve a balance between the high refractive index and the high Abbe number. The balance between refractive index and Abbe number is also an urgent problem that needs to be solved.

The present invention aims to solve the above problems.

In response to the above-described problems, the present invention provides a polythiol composition, a polymerizable composition for optical materials, and a method for producing the same. By introducing the thiol compound represented by formula (1) into the polythiol composition, a certain amount of polythiol composition component is added, which can affect the reaction activity in the pre-polymerization reaction of the polythiol composition and the isocyanate compound, This effectively reduces the polymerization reaction rate, enables effective control of viscosity at the beginning of the polymerization reaction, extends the working time of the next process, and effectively controls the balance of the refractive index and Abbe number.

The technical solutions adopted in the present invention are as follows:

A polythiol composition comprising a thiol compound represented by Formula (1) and a compound represented by Formula (2), where the formula for the total amount of the thiol compound represented by Formula (1) and the compound represented by Formula (2) is ( The proportion of the thiol compound represented by 1) is 0.005% to 6%. The preferred ratio is 0.01%-4%, more preferably 0.05%-2%. If the ratio is low, the viscosity of the pre-polymerization system cannot be controlled. If the ratio is high, the viscosity of the system will be too weak and the reaction time will be long, which will affect production efficiency; If the ratio is low or high, the Abbe number of the synthetic resin will decrease. Formula (1) is mercaptoethylthiomethyl-1,4-dithian and Formula (2) is 2,3-dithio(2-mercapto)-1-propanethiol,

A polymerizable composition for optical materials comprising a polythiol composition, an isocyanate compound, a catalyst, a UV absorber, and a mold release agent.

The mass ratio of polythiol composition to isocyanate is 1:2-0.5, preferably 1:1.8-0.7, more preferably 1:1.5-0.9; The dosage of catalyst is 0.01%-2%, preferably 0.05%-1.5%, more preferably 0.08%-1% of the total mass of polythiol composition and isocyanate; The dosage of UV absorber is 0.01%-2%, preferably 0.05%-1%, more preferably 0.08%-1% of the total mass of polythiol composition and isocyanate; The dosage of the release agent is 0.01%-2%, preferably 0.05%-1%, more preferably 0.08%-1% of the total mass of polythiol composition and isocyanate.

Preferably, the isocyanate is tetramethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, norbornene diisocyanate, m-xylylene diisocyanate, tetramethyl m-xylylene diisocyanate, Dithiodipropyl diisocyanate, dithiodiethyl diisocyanate, 2,5-diisocyanatomethylthiophene, 2,5-diisocyanatomethyl-1,4-dithiane, 2,5-diisocyane Ito-1,4-dithianate, thiodihexyl diisocyanate, thiodipropyl diisocyanate, bis(isocyanatomethyl)adamantane, bis(isocyanatomethyl)tetrahydrothiophene, 2,6- Bis(isocyanatomethyl)naphthalene, 1,5-naphthalene diisocyanate, diethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine triisocyanate, tolylene diisocyanate, o-tolidine diisocyanate, diphenylmethane It is selected from one or more of phosphorus diisocyanate, diphenyl ether diisocyanate, triphenylmethane triisocyanate, hydrogenated xylene diisocyanate, and xylene diisocyanate. Preferably, the isocyanate is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate and m-xylylene diisocyanate. More preferably, the isocyanate is selected from one of isophorone diisocyanate, norbornene diisocyanate and m-xylylene diisocyanate.

Preferably, the catalyst is one of dibutyltin dichloride, butyltin trichloride, octyltin trichloride, diphenylgermanium dichloride and triphenylantimony dichloride, preferably dibutyltin dichloride, octyltin trichloride and selected from diphenylgermanium dichloride, more preferably from dibutyltin dichloride and octyltin trichloride.

Preferably, the UV absorber is selected from UV326, UV329, UV531, UV-9, UV-541. Preferably, it is one of UV326, UV329, and UV-541, and more preferably, it is one of UV326 and UV329.

Preferably, the mold release agent is selected from one of isopropyl phosphate, dibutyl phosphate, octyl phosphate, isodecyl phosphate, lauryl polyoxyethylene ether phosphate, nonylphenol polyoxyethylene ether phosphate and polyphosphate. Preferably it is one of dibutyl phosphate, octyl phosphate, lauryl polyoxyethylene ether phosphate, nonylphenol polyoxyethylene ether phosphate and polyphosphate, more preferably dibutyl phosphate, lauryl polyoxyethylene ether phosphate and polyphosphate. It is one of the

Manufacturing method of optical material: The optical material is manufactured by curing with a polymerizable composition for optical material to obtain an optical material, during which the viscosity at the beginning of the polymerization reaction is ≤60mpa.s, and this viscosity is maintained for ≥1.5h. You can.

When the viscosity is ≤50mpa.s in the initial stage of polymerization reaction, this viscosity can be maintained for ≥2.5h; When the viscosity is ≤45mpa.s in the initial stage of the polymerization reaction, this viscosity can be maintained for ≥3h. The lower the reaction activity, the smaller the reaction rate, the lower the viscosity and the longer the reaction time required; The higher the reaction activity, the faster the reaction speed, the higher the viscosity and the shorter the reaction time, so by adjusting the viscosity at the beginning of the polymerization reaction, the adjustment work time can be extended and production efficiency can be ensured at the same time, avoiding the appearance of spray materials. Effectively eliminates material streaking in finished products, improves product qualification rate and excellent rate.

Compared to a single polythiol compound, in the present invention, the polythiol composition introduces a monofunctional thiol compound represented by formula (1), thereby reducing the concentration of reactive groups per volume, reducing the probability of intergroup reaction during the polymerization reaction, and thus Effectively reduce the polymerization reaction rate, effectively control the viscosity at the initial stage of the polymerization reaction, extending the working time and making the reaction easier; By introducing a molecularly well-organized, small, dense, and structurally stable ring of the thiol compound represented by Formula (1) into a polythiol composition, the Abbe number of the compound can be effectively increased.

The technical solution of the present invention is to effectively control the reactivity and reaction rate, adjust the viscosity of the pre-polymerization system, extend the working time of the next process, and at the same time provide excellent properties as well as high Abbe number and high refractive index. You can get materials. The optical material obtained through the technical solution of the present invention not only secures a high refractive index while effectively increasing the Abbe number, but also has excellent properties such as high glass transition temperature and high impact strength, satisfying customer needs and providing significant social and economic benefits. It has value.

By adding a specific amount of polythiol composition, the present invention can affect the reaction activity in the polymerization reaction of the polythiol composition with the isocyanate compound. The optical material manufactured by the present invention not only extends the working time and allows the reaction to be performed more easily and simply by controlling the viscosity at the beginning of the polymerization reaction (pre-polymerization), but also has a high refractive index and high Abbe number. , it has excellent optical properties with a high glass transition temperature and excellent mechanical properties. The optical material of the present invention can be used in the field of manufacturing a variety of high-precision optical materials such as optical glass, optical lenses, optical filters, LED packaging materials, high-reflection coatings, optoelectronic devices and many other fields of application, meeting customer requirements. and has great social and economic value.

It is included in the content of the present invention.

Specific Embodiments

The description set forth below is not intended to limit the invention, but rather to provide further explanation of the invention, along with specific embodiments, to enable those skilled in the art to further understand the invention, and any techniques based on the principles described herein. is within the scope of the present invention.

Viscosity: Tested using a digital viscometer (NDJ-5S).

Refractive Index: Tested using a multi-wavelength Abbe refractometer (DR-M4) at 20°C.

Abbe number: tested using a multi-wavelength Abbe refractometer (DR-M4).

Glass transition temperature: tested using a DSC-3 differential scanning calorimeter at a ramp rate of 10° C./min.

The polythiol compound of formula (1) is mercaptoethylthiomethyl-1,4-dithian, and the compound of formula (2) is 2,3-dithio(2-mercapto)-1-propanethiol.

Embodiment 1

A method of manufacturing an optical material, the steps are as follows:

(1) Pour 1 g of dibutyltin dichloride, 0.08 g of UV326, 0.09 g of dibutyl phosphate and 52 g of hexamethylene diisocyanate into the reaction flask in proportion, stir and mix uniformly at 15°C for 1 hour;

(2) 48 g of polythiol composition (a polythiol composition containing a thiol compound represented by Formula (1), a compound represented by Formula (2), and the thiol compound represented by Formula (1) are the total mass of the polythiol composition. (accounts for 0.05% of) into the reaction flask and mix well;

(3) After mixing uniformly in step (2), vacuum degassing for 20 minutes to obtain the mixture, check the viscosity of the mixture, inject it into a glass mold within a certain time, and then place the glass mold in an oven at 80°C for 28 hours. Harden. After curing, the lens is demolded and an optical material product is obtained.

Embodiment 2

A method of manufacturing an optical material, the steps are as follows:

(1) 0.08 g of dibutyltin dichloride, 0.1 g of UV329, 0.1 g of lauryl polyoxyethylene ether phosphate and 52 g of isophorone diisocyanate were poured into the reaction flask in proportion and stirred at 20°C for 1.5 hours. Mix evenly;

(2) 48 g of polythiol composition (a polythiol composition containing a thiol compound represented by Formula (1), a compound represented by Formula (2), and the thiol compound represented by Formula (1) are the total mass of the polythiol composition. (accounts for 1% of) into the reaction flask and mix well;

(3) After mixing uniformly in step (2), vacuum degassing for 20 minutes to obtain a mixture, check the viscosity of the mixture, inject it into a glass mold within a certain time, and then place the glass mold in an oven at 100°C for 24 hours. Harden. After curing, the lens is demolded and an optical material product is obtained.

Embodiment 3

A method of manufacturing an optical material, the steps are as follows:

(1) Pour 0.09 g of dibutyltin dichloride, 0.09 g of UV326, 0.08 g of octyl phosphate and 52 g of norbornene diisocyanate into the reaction flask in proportion, stir and mix evenly at 18°C for 1 hour. ;

(2) 48 g of polythiol composition (a polythiol composition containing a thiol compound represented by Formula (1), a compound represented by Formula (2), and the thiol compound represented by Formula (1) are the total mass of the polythiol composition. (accounts for 2% of) into the reaction flask and mix well;

(3) After mixing uniformly in step (2), vacuum degassing for 20 minutes to obtain a mixture, check the viscosity of the mixture, inject it into a glass mold within a certain time, and then place the glass mold in an oven at 120°C for 20 hours. Harden. After curing, the lens is demolded and an optical material product is obtained.

Embodiment 4

A method of manufacturing an optical material, the steps are as follows:

(1) Pour 0.05 g of octyltin trichloride, 1 g of UV-541, 2 g of polyphosphate, and 52 g of m-xylene diisocyanate into the reaction flask in proportion, stir at 15°C for 1.5 hours, and mix evenly. ;

(2) 48 g of polythiol composition (a polythiol composition containing a thiol compound represented by Formula (1), a compound represented by Formula (2), and the thiol compound represented by Formula (1) are the total mass of the polythiol composition. (accounts for 0.01% of) into the reaction flask and mix well;

(3) After mixing uniformly in step (2), vacuum degassing for 20 minutes to obtain a mixture, check the viscosity of the mixture, inject it into a glass mold within a certain time, and then place the glass mold in an oven at 90°C for 26 hours. Harden. After curing, the lens is demolded and an optical material product is obtained.

Embodiment 5

A method of manufacturing an optical material, the steps are as follows:

(1) Pour 1.5 g of diphenylgermanium dichloride, 0.05 g of UV329, 0.01 g of dibutyl phosphate and 52 g of hexamethylene diisocyanate into the reaction flask in proportion, stir and mix evenly at 16°C for 1 hour. ;

(2) 48 g of polythiol composition (a polythiol composition containing a thiol compound represented by Formula (1), a compound represented by Formula (2), and the thiol compound represented by Formula (1) are the total mass of the polythiol composition. (accounts for 4% of) into the reaction flask and mix well;

(3) After mixing uniformly in step (2), vacuum degassing for 20 minutes to obtain a mixture, check the viscosity of the mixture, inject it into a glass mold within a certain time, and then place the glass mold in an oven at 110°C for 22 hours. Harden. After curing, the lens is demolded and an optical material product is obtained.

Embodiment 6

A method of manufacturing an optical material, the steps are as follows:

(1) Pour 2g of dibutyltin dichloride, 0.01g of UV326, 1g of lauryl polyoxyethylene ether phosphate, and 52g of isophorone diisocyanate into a reaction flask in proportion, stir at 18°C for 1.5 hours, and stir evenly. Mix;

(2) 48 g of polythiol composition (a polythiol composition containing a thiol compound represented by Formula (1), a compound represented by Formula (2), and the thiol compound represented by Formula (1) are the total mass of the polythiol composition. (accounts for 0.005% of) into the reaction flask and mix well;

(3) After mixing uniformly in step (2), vacuum degassing for 20 minutes to obtain a mixture, check the viscosity of the mixture, inject it into a glass mold within a certain time, and then place the glass mold in an oven at 120°C for 18 hours. Harden. After curing, the lens is demolded and an optical material product is obtained.

Embodiment 7

A method of manufacturing an optical material, the steps are as follows:

(1) Pour 0.01 g of octyltin trichloride, 2 g of UV329, 0.05 g of octyl phosphate and 52 g of norbornene diisocyanate into the reaction flask in proportion, stir and mix uniformly at 20°C for 1 hour;

(2) 48 g of polythiol composition (a polythiol composition containing a thiol compound represented by Formula (1), a compound represented by Formula (2), and the thiol compound represented by Formula (1) are the total mass of the polythiol composition. (accounts for 6% of) into the reaction flask and mix well;

(3) After mixing uniformly in step (2), vacuum degassing for 20 minutes to obtain a mixture, check the viscosity of the mixture, inject it into a glass mold within a certain time, and then place the glass mold in an oven at 100°C for 25 hours. Harden. After curing, the lens is demolded and an optical material product is obtained.

Comparative Embodiment 1

A method of manufacturing an optical material, the steps are as follows:

(1) Pour 1 g of dibutyltin dichloride, 0.08 g of UV326, 0.09 g of dibutyl phosphate and 52 g of hexamethylene diisocyanate into the reaction flask in proportion, stir and mix uniformly at 15°C for 1 hour;

(2) Add 48 g of the compound represented by formula (2) into the reaction flask and mix well;

(3) After mixing uniformly in step (2), vacuum degassing for 20 minutes to obtain a mixture, check the viscosity of the mixture, inject it into a glass mold within a certain time, and then place the glass mold in an oven at 80°C for 28 hours. Harden. After curing, the lens is demolded and an optical material product is obtained.

Comparative Embodiment 2

A method of manufacturing an optical material, the steps are as follows:

(1) Pour 0.08 g of dibutyltin dichloride, 0.1 g of UV326, 0.1 g of dibutyl phosphate and 52 g of hexamethylene diisocyanate into the reaction flask in proportion, stir at 15°C for 1 hour and mix evenly. ;

(2) 48 g of polythiol composition (a polythiol composition containing a thiol compound represented by Formula (1), a compound represented by Formula (2), and the thiol compound represented by Formula (1) are the total mass of the polythiol composition. (accounting for 10% of) into the reaction flask and mix well;

(3) After mixing uniformly in step (2), vacuum degassing for 20 minutes to obtain a mixture, check the viscosity of the mixture, inject it into a glass mold within a certain time, and then place the glass mold in an oven at 120°C for 20 hours. Harden. After curing, the lens is demolded and an optical material product is obtained.

Comparative Embodiment 3

A method of manufacturing an optical material, the steps are as follows:

(1) Pour 1 g of dibutyltin dichloride, 0.08 g of UV326, 0.09 g of dibutyl phosphate and 52 g of hexamethylene diisocyanate into the reaction flask in proportion, stir and mix uniformly at 15°C for 1 hour;

(2) Add 48 g of the mixture to the reaction flask (the mixture includes the compound represented by formula (3) and 4-mercaptomethyl-1,8-dimercapto-3,6-dithioctane, where The compound represented by formula (3) accounts for 1.5% of the total mass of the mixture) and mix well. The structure of the compound of formula (3) is as follows:

R1 represents CH ₂ SCH ₂ CH ₂ SH and R ₂ represents hydrogen;

(3) After mixing uniformly in step (2), vacuum degassing for 20 minutes to obtain the mixture, check the viscosity of the mixture, inject it into a glass mold within a certain time, and then place the glass mold in an oven at 80°C for 28 hours. Harden. After curing, the lens is demolded and an optical material product is obtained.

The performance test results of the optical resin lenses prepared in Embodiments 1-7 and Comparative Examples 1-3 are shown in the table below:

Initial viscosity of polymerization reaction/mpa.s injection time/h refractive index Abesu Glass transition temperature/℃ Embodiment 1 45 3.0 1.6620 33.5 88.0 Embodiment 2 40 3.5 1.6625 33.0 88.0 Embodiment 3 35 4.0 1.6630 34.0 87.0 Embodiment 4 48 2.5 1.6620 33.0 87.8 Embodiment 5 35 4.0 1.6629 33.9 86.9 Embodiment 6 52 1.8 1.6618 32.9 87.5 Embodiment 7 25 6.0 1.6625 33.4 86.1 Comparative Embodiment 1 55 1.5 1.6610 31.5 85.0 Comparative Embodiment 2 20 8.0 1.6605 31.0 84.0 Comparative Embodiment 3 65 1.3 1.6610 31.5 85.0

As shown in the table above, the Abbe number of the optical material prepared in Embodiment 1-7 is ≥32.9, which is significantly higher than the Abbe number of the optical material prepared in Comparative Embodiment 1-3, and in Example 1-7 The glass transition temperature of the prepared optical material is ≧86.1, which is significantly higher than the glass transition temperature of the optical material prepared in Comparative Embodiments 1-3, from which it can be seen that the addition amount of the thiol represented by Formula (1) is too much or too much. If it is small, it affects not only the glass transition temperature but also increases the Abbe number; In Comparative Embodiment 1, when the added amount of the thiol compound represented by Chemical Formula (1) is 0, the viscosity at the beginning of the polymerization reaction is high, the working time is short, and production abnormalities such as material spraying are likely to occur, which leads to material streaks and material in the finished product. will cause other problems; In Comparative Embodiment 2, it was found that if the added amount of the thiol compound represented by Chemical Formula (1) was too large and the viscosity at the beginning of the polymerization reaction was low, production efficiency was affected. Embodiment 1-7 adds the thiol compound represented by Chemical Formula (1) at an appropriate ratio in the initial stage of the polymerization reaction, which affects the reaction rate and viscosity, to appropriately extend the working time, ensure efficiency, and Avoids streaking problems.

By adding a specific amount of polythiol composition, the present invention can affect the reaction activity in the polymerization reaction of the polythiol composition with the isocyanate compound. The optical material manufactured by the present invention not only extends the working time and allows the reaction to be performed more easily and simply by controlling the viscosity at the beginning of the polymerization reaction (pre-polymerization), but also has a high refractive index and high Abbe number. , it has excellent optical properties with a high glass transition temperature and excellent mechanical properties. The optical material of the present invention can be used in the field of manufacturing a variety of high-precision optical materials such as optical glass, optical lenses, optical filters, LED packaging materials, high-reflection coatings, optoelectronic devices and many other fields of application, meeting customer requirements. and has great social and economic value.

Claims (7)

A polythiol composition comprising a thiol compound represented by formula (1) and a compound represented by formula (2), wherein the thiol compound represented by formula (1) and the compound represented by formula (2) A polythiol composition in which the ratio of the thiol compound represented by Formula (1) to the total amount is 0.005% to 6%,

. According to claim 1,
A polythiol composition, characterized in that the ratio of the thiol compound represented by Formula (1) to the total amount of the thiol compound represented by Formula (1) and the compound represented by Formula (2) is 0.01% to 4%. According to claim 2,
A polythiol composition, characterized in that the ratio of the thiol compound represented by Formula (1) to the total amount of the thiol compound represented by Formula (1) and the compound represented by Formula (2) is 0.05% to 2%. A polymerizable composition for optical materials comprising a polythiol composition, an isocyanate compound, a catalyst, a UV absorber, and a mold release agent. According to claim 4,
The mass ratio of polythiol composition to isocyanate is 1:2-0.5, the dosage of catalyst is 0.01%-2% of the total mass of polythiol composition and isocyanate, the dosage of UV absorber is 0.01%-2% of the total mass of polythiol composition and isocyanate. A polymerizable composition for optical materials, characterized in that the amount of the release agent is 0.01%-2% of the total mass of the polythiol composition and the isocyanate. According to claim 5,
The mass ratio of polythiol composition to isocyanate is 1:1.8-0.7, the dosage of catalyst is 0.05%-1.5% of the total mass of polythiol composition and isocyanate, the dosage of UV absorber is 0.05%-1.5% of the total mass of polythiol composition and isocyanate. 0.05%-1% of the mass, and the dosage of the release agent is 0.05%-1% of the total mass of the polythiol composition and the isocyanate. A method of manufacturing an optical material, characterized in that the optical material is manufactured by curing the polymerizable composition for an optical material of claim 4, wherein the viscosity at the initial stage of the polymerization reaction is ≤60 mpa.s.